JPWO2018038189A1 - 1-phenyl-3-carbamoyl urea compound and use thereof - Google Patents

Abstract

The present invention provides a compound represented by the formula (1): The compound has an excellent control activity against plant diseases and is useful as an active ingredient of a plant disease control agent.

Description

This patent application claims the priority and benefit under the Paris Convention based on Japanese Patent Application 2016-165423 (filed on August 26, 2016), which is described in the above application by reference. The entire content of which is incorporated herein by reference.
The present invention relates to 1-phenyl-3-carbamoyl urea compounds and uses thereof.

  Patent Document 1 describes N- [4-chloro-2-fluoro-5- {2- (ethoxycarbonyl) methoxy-3-pyridyloxy} phenyl] acetamide.

European Patent No. 1122244

  An object of the present invention is to provide a compound having excellent control efficacy against plant diseases.

で示される化合物（以下、本発明化合物と記す）。
［２］ ［１］に記載の化合物を含有する植物病害防除剤（以下、本発明防除剤とも記す）。
［３］ ［１］に記載の化合物の有効量を植物又は植物を栽培する土壌に処理することによる、植物病害の防除方法。
［４］ 植物病害を防除するための［１］に記載の化合物の使用。As a result of examining to find a compound having excellent control activity against plant diseases, the present inventor has found that a compound represented by the following formula (1) has excellent control activity against plant diseases.
That is, the present invention is as follows.
[1] Formula (1):

And a compound represented by (hereinafter, referred to as a compound of the present invention).
[2] A plant disease control agent containing the compound according to [1] (hereinafter also referred to as the present control agent).
[3] A method for controlling plant diseases by treating an effective amount of the compound according to [1] on a plant or a soil for cultivating a plant.
[4] Use of the compound according to [1] for controlling plant diseases.

  According to the present invention, plant diseases can be controlled.

  The control agent of the present invention usually mixes the compound of the present invention with a solid carrier, liquid carrier, oil and / or surfactant and the like, and if necessary, an adjuvant for formulation such as a fixing agent, a dispersing agent and a stabilizer is added Then, it is formulated and used in wettable powders, water dispersible granules, flowables, granules, dry flowables, emulsions, aqueous solutions, oils, smokes, aerosols, microcapsules and the like. These preparations contain the compound of the present invention in a weight ratio of usually 0.1 to 99%, preferably 0.2 to 90%.

As a solid carrier, for example, clays (eg, kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, fuvasami clay, bentonite, acid clay), talcs and other inorganic minerals (eg, sericite, quartz powder, sulfur powder, activated carbon) And fine powders or granules such as calcium carbonate and hydrated silica).
Examples of the liquid carrier include water, alcohols (methanol, ethanol etc.), ketones (acetone, methyl ethyl ketone etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, methyl naphthalene etc.), aliphatic hydrocarbons ( Hexane, cyclohexane, kerosene etc., esters (ethyl acetate, butyl acetate etc.), nitriles (acetonitrile, isobutyl nitrile etc.), ethers (diisopropyl ether etc.), amides (dimethylformamide, dimethylacetamide etc.), sulfoxide And the like (dimethyl sulfoxide and the like).

  As surfactants, for example, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and their polyoxyethylene derivatives, polyoxyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohols Derivatives are included.

  Other pharmaceutical auxiliaries include, for example, fixing agents, dispersing agents and stabilizers, and specifically, casein, gelatin, polysaccharides (eg, starch, arabia gum, cellulose derivatives, alginic acid), lignin derivatives, bentonite , Saccharides, synthetic water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA ( (A mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid and the like.

  Examples of oils and surfactants that can be used in combination with the compound of the present invention include Nimbus (R), Assist (R), Aureo (R), Iharol (R), and Silwet L-77 (R). ), BreakThru (registered trademark), Sundance II (registered trademark), Induce (registered trademark), Penetrator (registered trademark), AgriDex (registered trademark), Lutensol A8 (registered trademark), NP-7 (registered trademark), Triton (registered trademark) Trademarks, Nufilm (R), Emulgator NP7 (R), Emulad (R), TRITON X 45 (R), AGRAL 90 (R), AGROTIN (R), ARPON (R), EnSpra N (R), and BANOLE (registered trademark).

The compound of the present invention is applied as a control agent of the present invention. The method of applying the control agent of the present invention is not particularly limited as long as the control agent of the present invention can be substantially applied. For example, treatment of plants such as foliage application, soil treatment, etc. The treatment to the cultivation place of a plant, the treatment to seeds, such as seed disinfection, etc. are mentioned.
The amount of the compound of the present invention to be treated in the control method of the present invention varies depending on the type of plant to be treated, type and frequency of occurrence of plant disease to be controlled, formulation form, treatment time, treatment method, treatment place, weather conditions, etc. However, when processing on the stems and leaves of plants or in the soil where plants are grown, the amount of the compound of the present invention is usually 1 to 500 g per 1000 m ² .
Emulsions, wettable powders, flowables and the like are usually treated by diluting with water and spraying. In this case, the concentration of the compound of the present invention is usually 0.0005 to 2% by weight. Powders, granules and the like are usually treated as such without dilution.

  The compounds of the present invention can be used as agents for controlling plant diseases in agricultural lands such as fields, paddy fields, lawns, orchards.

  Examples of plant diseases that can be controlled by the compound of the present invention include diseases derived from plant pathogens such as filamentous fungi and bacteria, and specific examples thereof include the following. The parentheses show the scientific names of the pathogens that cause the disease.

Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), dreadling (Gibberella fujikuroi), yellow dwarf (Sclerophthora macrospora); wheat powdery mildew (Blumeria graminis) of wheat ), Fusarium head blight (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), red rust (Puccinia recondita), red snowfever (Microdochium nivale) Microdochium majus), snow blight scleroderma (Typhula incarnata, Typhula ishikariensis), naked scab (U. stilago tritici), scab (Tilletia caries, Tilletia controversa), scab (Pseudocercosporella herpotrichoidestagona) nodorum, yellow spot (Pyrenophora tritici-repentis), rhizoctonia spp. seedling blight (Rhizoctonia solani), blight (Gaeumannomyces graminis); Powdery mildew (Blumeria graminis), Fusarium head blight (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), red rust (Puccinia hordei) Rust disease (Puccinia hordei), naked scab (Ustilago nuda), scab (Rhynchosporium secalis), web blight (Pyrenophora teres), spot disease (Cochliobolus sativus), plague (Pyrenophora graminea), Lamulalia leaf spot disease Seedlings blight (Rhizoctonia solani) by Ramularia collo-cygni), Rhizoctonia sp .; Rust (Puccinia sorghi), southern rust (Puccinia polysora), scab (Setosphaeria turcica), tropical rust (Physopella) zeae), sesame leaf blight (Cochliobolus heterostrophus), anthracnose (Colletotrichum graminicola), gray leaf spot disease (Cercospora zeae-maydis), brown spot (Kabatiella zeae), Aeospha area leaf spot disease (Phaeosphaeria maydis), diplodia disease (Stenocarpella maydis, Stenocarpella macrospora), Stochlot's disease (Fusarium graminearum, Fusarium verticilioides, Colletotrichum graminicola), scab disease (Ustilago maydis); Colletotrichum gossypii), mildew (Ramularia areola), black spot (Alternaria macrospora, Alternaria gossypii), Black root rot (Thielaviopsis basicola) by Thielaviopsis spp. (Hemileia vastatrix of coffee), leaf spot disease (Cercospora) coffeicola); sclerotiosis of rapeseed (Sclerotinia sclerotiorum), black spot (Alternaria brassicae), root rot (Phoma lingam); sugarcane rust (Puccinia melanocephala, Puccinia kuehnii); sunflower rust (Puccinia helianthi) Downy mildew (Plasmopara halstedii); Citrus black spot (Diaporthe citri), scab (Elsinoe fawcetti) ), Fruit rot (Penicillium digitatum, Penicillium italicum), plague (Phytophthora parasitica, Phytophthora citrophthora); Alternaria alternata apple pathotype, scab (Venturia inaequalis), anthracnose (Glomerella cingulata), brown spot (Diplocarpon mali), ring blight (Botryosphaeria berengeriana), plague (Phytophtora cactorum); scab (Venturia nashicola of pear) , Venturia pirina), black spot (Alternaria alternata Japanese pear pathotype), red star disease (Gymnosporangium haraeanum); peach scab (Monilinia fructicola), scab (Cladosporium carpophilum), phomopsis putrefaction (Phomopsis sp.); Black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), Laclot disease (Guignardia bidwellii), downy mildew (Plasmoparabiticola); anthracnose of oyster (Gloeosporium kaki), deciduous disease (Cercospora kaki, Mycosphaerella nawae); Anthracnose of Cucurbita (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), spine blight (Didymella bryoniae), brown spot (Corynespora cassiicola), spine blight (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.), Seedling blight (Pythium) sp.); Ring blight of tomato (Alternaria solani), leaf blight (Cladosporium fulvum), leaf blight (Pseudocercospora fuligena), plague (Phytophthora infestans), powdery mildew (Leveillula taurica); Phomopsis vexans), powdery mildew (Erysiphe cichoracearum); black spot (Alternaria japonica) of Brassicaceae, white spot (Cercosporella brassicae), scab disease (Plasmodiophora brassicae), downy mildew (Peronospora parasitica) Rust disease of green onion (Puccinia allii); purpuric disease of soybean (Cercospora kikuchii), black spot disease (Elsinoe glycines), black spot disease (Diaporthe phaseolorum var. Sojae), rust disease (Phakopsora pachyrhizi), brown ring disease (Corynespora) cassiicola), anthracnose (Colletotrichum glycines, Colletotrichum truncatum), leaf blight (Rhizoctonia solani), brown leaf blight (Septoria glycines), blight disease (Cercospora sojina), sclerotis disease (Sclerotinia sclerotiorum), powdery mildew (Microscopica) ), Downy mildew (Phytophthora sojae), downy mildew (Peronospora manshurica), sudden death (Fusarium virguliforme); sclerotis sclerotis (Sclerotinia sclerotiorum), rust (Uromyces appendiculatus), horny mildew (Phaeoisariopsis griseola), Anthracnose (Colletotrichum lindemuthianum); peanut blight (Cercospora personata), brown spot (Cercospora arachidicola), white scab (Sclerotium rolfsii); powdery mildew of pea (Erysi) phe pisi); potato blight (Alternaria solani), blight (Phytophthora infestans), green rot (Phytophthora erythroseptica), powdery mildew (Spongospora subterranean f. sp. subterranea), half body wilt (Verticillium albo-atrum) , Verticillium dahliae, Verticillium nigrescens); powdery mildew of strawberries (Sphaerotheca humuli); tea scab (Exobasidium reticulatum), scab (Elsinoe leucospila), rot blotch (Pesalotiopsis sp.), Anthracnose (Colletotrichum theae) -Sinensis of tobacco; Alternaria longipes of tobacco, Colletotrichum tabacum, Downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae); Brown disease of sugar beet (Cercospora beticola), leaf rot (Thatephorusus) cucumeris), root rot (Thanatephorus cucumeris), black rot (Aphanomyces cochlioides), rust (Uromyces betae); rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannos) a); Chrysanthemum brown spot (Septoria chrysanthemi-indici), white rust (Puccinia horiana); Onion mildew (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa), gray rot (Botrytis allii), small fungus Nuclear rot (Botrytis squamosa); sclerotis of various crops (Sclerotinia sclerotiorum); Japanese radish (Alternaria brassicicola); Shiba's Dollar spot disease (Sclerotinia homoeocarpa), Shiva brown patch disease and large patch disease Rhizoctonia solani); and Sigatoka disease of bananas (Mycosphaerella fijiensis, Mycosphaerella musicola).
Seed disease or early growth of various crops caused by Aspergillus spp., Penicillium sp., Fusarium sp., Gibberella sp., Tricoderma sp., Thieloviopsis sp., Rhizopus sp., Rhizopus sp., Mucor sp. Diseases of Virus diseases of various crops mediated by Polymixa genus or Olpidium genus etc.
Seedling blight of rice (Burkholderia plantarii); cucumber blight (Phytophthora capsici), seedling blight (Pythium ultimum) and spotted blight (Pseudomonas syringae pv. Lachrymans); Citrus rot (Xanthomonas citiri); soft rot of Chinese cabbage (Erwinia carotovora) etc.

  The present invention will be more specifically described by way of production examples and test examples, but the present invention is not limited to these examples.

  First, a manufacturing example is shown.

４−クロロ−２−フルオロ−５−｛２−（エトキシカルボニル）メトキシ−３−ピリジルオキシ｝アニリン０．３０ｇ（０．８８ｍｍｏｌ）、ジメチルホルムアミド１ｍＬ、及び水２ｍＬの混合物に、１−ニトロ−３−カルバモイル尿素０．１７ｇ（１．１ｍｍｏｌ）を加え、還流下１０時間撹拌した。この混合物を室温へ冷却した後、水を加え、酢酸エチルで抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付し、本発明化合物４８ｍｇ（０．１１ｍｍｏｌ）を得た。
¹Ｈ−ＮＭＲ （ＣＤＣｌ₃） δ (ppm)： ９．３０ （１Ｈ， ｓ）， ７．８８ （１Ｈ， ｄ， Ｊ ＝ ７．６ Ｈｚ）， ７．８５ （１Ｈ， ｄｄ， Ｊ ＝ ５．２， １．６ Ｈｚ）， ７．２２ （１Ｈ， ｄ， Ｊ ＝ １０．０ Ｈｚ）， ７．０６ （１Ｈ， ｄｄ， Ｊ ＝ ７．８， １．６ Ｈｚ）， ６．８７ （１Ｈ， ｄｄ， Ｊ ＝ ７．８， ５．２ Ｈｚ）， ４．９６ （２Ｈ， ｓ）， ４．２１ （２Ｈ， ｑ， Ｊ ＝ ６．４ Ｈｚ） ， １．２６ （３Ｈ， ｔ， Ｊ ＝ ７．２ Ｈｚ）．
ＥＳＩ−ＭＳ（ｐｏｓｉ）：４２７［Ｍ＋Ｈ］⁺ Production example

4-chloro-2-fluoro-5- {2- (ethoxycarbonyl) methoxy-3-pyridyloxy} aniline 0.30 g (0.88 mmol) of aniline, 1 mL of dimethylformamide, and 2 mL of water in a mixture of 1-nitro-3 0.17 g (1.1 mmol) of -carbamoyl urea was added, and the mixture was stirred under reflux for 10 hours. The mixture was cooled to room temperature, water was added and extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 48 mg (0.11 mmol) of the present compound.
¹ H-NMR (CDCl ₃ ) δ (ppm): 9.30 (1 H, s), 7.88 (1 H, d, J = 7.6 Hz), 7. 85 (1 H, dd, J = 5. 2, 1.6 Hz), 7.22 (1 H, d, J = 10.0 Hz), 7.06 (1 H, dd, J = 7.8, 1.6 Hz), 6.87 (1 H, 1 H, d dd, J = 7.8, 5.2 Hz), 4.96 (2H, s), 4.21 (2H, q, J = 6.4 Hz), 1.26 (3H, t, J = 7) .2 Hz).
ESI-MS (posi): 427 [M + H] ⁺

  Next, test examples are shown.

Test Example 1 Control Test Against Phytophthora capsici The compound of the present invention 4.5 mg was diluted with 100 μL of dimethyl sulfoxide. After 1 μL of the diluted solution was dispensed into a titer plate (96 wells), 150 μL of potato juice liquid medium (PDB medium) containing zoospores of Phytophthora capsici was dispensed. The plate was cultured at 27 ° C. for 3 days to grow C. epizoa and then the absorbance at 600 nm of each well of the titer plate was measured to determine the degree of growth of C. faecalis. The potency of the compound of the present invention was 80% or more when the potency was calculated using “Formula 1” based on the degree of growth.
"Formula 1"
Efficacy = 100 × (X-Y) / X
X: Viability of bacteria in the untreated zone Y: Viability of bacteria in the treated zone In the untreated zone in this test example, dimethyl sulfoxide is dispensed instead of the dimethyl sulfoxide diluted solution containing the compound of the present invention Except for the test area, which was conducted under the same conditions as the treatment area.
On the other hand, the same test was carried out using N- [4-chloro-2-fluoro-5- {2- (ethoxycarbonyl) methoxy-3-pyridyloxy} phenyl] acetamide described in European Patent No. 1122244. As a result, its efficacy was less than 50%.

  The compound of the present invention has a controlling effect on plant diseases and is useful as an active ingredient of plant disease controlling agents.

Claims (4)

Formula (1):

A compound represented by   The plant disease control agent containing the compound of Claim 1.   A method for controlling plant diseases by treating an effective amount of the compound according to claim 1 to a plant or a soil for cultivating a plant.   Use of the compounds according to claim 1 for controlling plant diseases.